크라운 에테르를 반복 사용 기능의 상이동 촉매(phase transfer catalyst ; PTC)로 유도하기 위해 고분자 물질로 지지된 크라운 에테르(polymer-supported crown ether ; Ps-CE)류를 합성하고, 이들 Ps-CE(solid phase)를 이용하여 액-고-액 3상 불균일계에서의 1-bromooctane(유기층)의 iodide(수용층) 친핵 치환 반응속도를 측정하고 그 상이동 촉매능을 연구검토하였다. Ps-CE류는 hydroxymethyl기를 지니는 크라운 에테르류를 합성한 후 이를 1∼2% cross-linked chloromethylated polystyrene 에그라프트시켜 제조하였다. 3상 불균일계치환반응은 반응기질의 농도에 의존하는 유사 일차반응이었고 반응속도상수$(k_{obsd})$는 사용한 촉매량에 비례하였으며, 가교밀도, 온도, 용매 등에 영향을 받음을 알 수 있었다. Ps-CE의 촉매능을 구조적으로 유사한 가용성 크라운 에테르의 촉매능과 비교하였으며, 반응 후 단순히 여과분리하고 이를 PTC로서 반복사용하였을때 촉매능의 감소없이 재사용이 가능함을 알 수 있었다. 반응의 활성화 엔탈피 및 엔트로피는 각각 10∼20kcal <TEX>$mol^{-1}, 20~55eu.이었고 활성화 자유 에너지는 ∼30kcal mol^{-1}$,/TEX>이었다.
Polymer-supported crown ethers (Ps-CE) which can be used for phase-transfer catalyst (PTC) were synthesized for the purpose of allowing reusable function to ordinary crown ethers, and the kinetics of the liquid-solid-liquid triphase-catalyzed nucleophilic displacement reaction of iodide (aqueous phase) on 1-bromooctane (organic phase) using synthesized Ps-CE (solid) were studied. Ps-CE were obtained by grafting of hydroxymethyl crown ethers to 1~2% cross-linked chloromethylated polystyrene. All reactions followed a pseudo-first order dependency on the 1-bromooctane concentration and the observed rate constants $(k_{obsd})$ were linearly related to the molar equivalents of Ps-CE, and were subjected to the influence of cross-linking density of polymer backbone, solvent and the reaction temperature. The catalytic activity of Ps-CE was also compared with that of structurally similar soluble crown ethers, and used Ps-CE were easily recovered after the reaction by simple filtration and could be reused without loss of catalytic activity in the same anionic displacement reaction. Enthalpies and entropies of activation associated with the displacement were 10~20kcal $mol^{-1}, 20~55eu. respectively, and the free energy of activation was ~30kcal mol^{-1}$.
